Quaternized ammonium salts of hydrocarbyl epoxides and use thereof as additives in fuels and lubricants

ABSTRACT

The present invention relates to novel quaternized ammonium salts of hydrocarbyl epoxides, to the preparation thereof and to the use thereof as a fuel additive and lubricant additive, such as, more particularly, as a detergent additive; for reducing or preventing deposits in the injection systems of direct injection diesel engines, especially in common rail injection systems, for reducing the fuel consumption of direct injection diesel engines, especially of diesel engines with common rail injection systems, and for minimizing power loss in direct injection diesel engines, especially in diesel engines with common rail injection systems; and as an additive for gasoline fuels, especially for operation of DISI engines.

The present invention relates to novel quaternized ammonium salts ofhydrocarbyl epoxides, to the preparation thereof and to the use thereofas a fuel additive and lubricant additive, such as, more particularly,as a detergent additive; for reducing or preventing deposits in theinjection systems of direct injection diesel engines, especially incommon rail injection systems, for reducing the fuel consumption ofdirect injection diesel engines, especially of diesel engines withcommon rail injection systems, and for minimizing power loss in directinjection diesel engines, especially in diesel engines with common railinjection systems; and as an additive for gasoline fuels, especially foroperation of DISI engines.

STATE OF THE ART

In direct injection diesel engines, the fuel is injected and distributedultrafinely (nebulized) by a multihole injection nozzle which reachesdirectly into the combustion chamber of the engine, instead of beingintroduced into a prechamber or swirl chamber as in the case of theconventional (chamber) diesel engine. The advantage of direct injectiondiesel engines lies in their high performance for diesel engines andnevertheless low fuel consumption. Moreover, these engines achieve avery high torque even at low speeds.

At present, essentially three methods are being used for injection ofthe fuel directly into the combustion chamber of the diesel engine: theconventional distributor injection pump, the pump-nozzle system(unit-injector system or unit-pump system), and the common rail system.

In the common rail system, the diesel fuel is conveyed by a pump withpressures up to 2000 bar into a high-pressure line, the common rail.Proceeding from the common rail, branch lines run to the differentinjectors which inject the fuel directly into the combustion chamber.The full pressure is always applied to the common rail, which enablesmultiple injection or a specific injection form. In the other injectionsystems, in contrast, only a smaller variation in the injection ispossible. Injection in the common rail is divided essentially into threegroups: (1.) pre-injection, by which essentially softer combustion isachieved, such that harsh combustion noises (“nailing”) are reduced andthe engine seems to run quietly; (2.) main injection, which isresponsible especially for a good torque profile; and (3.)post-injection, which especially ensures a low NO_(x) value. In thispost-injection, the fuel is generally not combusted, but insteadvaporized by residual heat in the cylinder. The exhaust gas/fuel mixtureformed is transported to the exhaust gas system, where the fuel, in thepresence of suitable catalysts, acts as a reducing agent for thenitrogen oxides NO_(x).

The variable, cylinder-individual injection in the common rail injectionsystem can positively influence the pollutant emission of the engine,for example the emission of nitrogen oxides (NO_(x)), carbon monoxide(CO) and especially of particulates (soot). This makes it possible, forexample, for engines equipped with common rail injection systems to meetthe Euro 4 standard theoretically even without additional particulatefilters.

In modern common rail diesel engines, under particular conditions, forexample when biodiesel-containing fuels or fuels with metal impuritiessuch as zinc compounds, copper compounds, lead compounds and other metalcompounds are used, deposits can form on the injector orifices, whichadversely affect the injection performance of the fuel and hence impairthe performance of the engine, i.e. especially reduce the power, but insome cases also worsen the combustion. The formation of deposits isenhanced further by further developments in the injector construction,especially by the change in the geometry of the nozzles (narrower,conical orifices with rounded outlet). For lasting optimal functioningof engine and injectors, such deposits in the nozzle orifices must beprevented or reduced by suitable fuel additives.

In the injection systems of modern diesel engines, deposits causesignificant performance problems. It is common knowledge that suchdeposits in the spray channels can lead to a decrease in the fuel flowand hence to power loss. Deposits at the injector tip, in contrast,impair the optimal formation of fuel spray mist and, as a result, causeworsened combustion and associated higher emissions and increased fuelconsumption. In contrast to these conventional “external” depositionphenomena, “internal” deposits (referred to collectively as internaldiesel injector deposits (IDID)) in particular parts of the injectors,such as at the nozzle needle, at the control piston, at the valvepiston, at the valve seat, in the control unit and in the guides ofthese components, also increasingly cause performance problems.Conventional additives exhibit inadequate action against these IDIDs.

U.S. Pat. No. 4,248,719 describes quaternized ammonium salts which areprepared by reacting an alkenylsuccinimide with a monocarboxylic esterand find use as dispersants in lubricant oils for prevention of sludgeformation. More particularly, for example, the reaction ofpolyisobutylsuccinic anhydride (PIBSA) with N,N-dimethylaminopropylamine(DMAPA) and quaternization with methyl salicylate is described. However,use in fuels, more particularly diesel fuels, is not proposed therein.

U.S. Pat. No. 4,171,959 describes quaternized ammonium salts ofhydrocarbyl-substituted succinimides, which are suitable as detergentadditives for gasoline fuel compositions. Quaternization is preferablyaccomplished using alkyl halides. Also mentioned are organicC₂-C₈-hydrocarbyl carboxylates and sulfonates. Consequently, thequaternized ammonium salts provided according to the teaching thereinhave, as a counterion, either a halide or a C₂-C₈-hydrocarbylcarboxylate or a C₂-C₈-hydrocarbyl sulfonate group.

EP-A-2 033 945 discloses cold flow improvers which are prepared byquaternizing specific tertiary monoamines bearing at least oneC₈-C₄₀-alkyl radical with a C₁-C₄-alkyl ester of specific carboxylicacids. Examples of such carboxylic esters are dimethyl oxalate, dimethylmaleate, dimethyl phthalate and dimethyl fumarate. Uses other than thatfor improvement of the CFPP value of middle distillates are notdemonstrated in EP-A-2 033 945.

WO 2006/135881 describes quaternized ammonium salts prepared bycondensation of a hydrocarbyl-substituted acylating agent and of anoxygen or nitrogen atom-containing compound with a tertiary amino group,and subsequent quaternization by means of hydrocarbyl epoxide incombination with stoichiometric amounts of an acid such as, moreparticularly, acetic acid. Further quaternizing agents claimed in WO2006/135881 are dialkyl sulfates, benzyl halides andhydrocarbyl-substituted carbonates, and dimethyl sulfate, benzylchloride and dimethyl carbonate have been studied experimentally.

WO 2008/060888 discloses quaternary ammonium salts ofpolyalkene-substituted amines which are used as detergent additives infuel compositions for reduction of intake system deposits. Preferredcompounds are prepared by hydroformylation of polyisobutene orchlorination of polyisobutene and subsequent reaction with a diamine,followed by the quaternization of the polyisobutenediamine thus obtainedby means of conventional quaternizing agents, such as dimethyl sulfate,benzyl chloride, or styrene epoxide/acid.

The quaternized compounds known to date are preparable with a relativelyhigh level of synthesis complexity. It was therefore an object of thepresent invention to provide quaternized fuel additives which arefirstly easier to prepare and secondly have satisfactory additiveproperties.

BRIEF DESCRIPTION OF THE INVENTION

It has now been found that, surprisingly, the above object is achievedby providing quaternized ammonium salts of hydrocarbyl epoxides and fuelcompositions and lubricant compositions additized therewith.

Surprisingly, the inventive additives, as illustrated especially by theappended use examples, are not just preparable in a simple manner fromthe corresponding hydrocarbyl epoxide precursors, but also surprisinglyexhibit satisfactory additive properties, such as, more particularly, inoperation in modern diesel engines.

DESCRIPTION OF FIGURES

FIG. 1 shows the running of the one-hour engine test cycle according toCEC F-098-08.

DETAILED DESCRIPTION OF THE INVENTION A1) Specific Embodiments

The present invention relates especially to the following embodiments:

-   1. A fuel composition or lubricant composition comprising, in a    majority of a customary fuel or lubricant, an effective proportion    of at least one reaction product comprising a quaternized nitrogen    compound, or a fraction thereof which comprises a quaternized    nitrogen compound and is obtained from the reaction product by    purification, said reaction product being obtainable by    -   reacting at least one hydrocarbyl epoxide of the general formula        I

-   -   -   in which        -   at least one of the R₁ and R₂ radicals is a straight-chain            or branched, saturated or unsaturated, long-chain            hydrocarbyl radical, e.g. polyalkylene radical, and the            other of the two radicals is optionally H or a short-chain            hydrocarbyl radical (especially C₁-C₄ alkyl); and        -   the R₃ and R₄ radicals are the same or different and are            each H or a short-chain hydrocarbyl radical (especially            C₁-C₄ alkyl);

    -   with at least one tertiary amine of the general formula II

R_(a)R_(b)R_(c)N  (II)

-   -   -   in which        -   R_(a), R_(b) and R_(c) are each independently a            straight-chain or branched, saturated or unsaturated,            optionally substituted hydrocarbyl radical, especially            short-chain hydrocarbyl radical, or alkyl or alkenyl,            especially C₁-C₂₄-alkyl or C₂-C₂₄-alkenyl, or two of the            R_(a), R_(b) and R_(c) radicals, together with the nitrogen            atom to which they are bonded, form an optionally            substituted heterocyclic ring, especially 5- to 7-membered,            saturated or unsaturated, nonaromatic or aromatic            heterocyclic ring, which may optionally bear at least one            further ring heteroatom such as O, S or N;

    -   and in the presence of at least one acid of the formula III

H⁺A⁻  (III)

-   -   -   in which        -   A⁻ is the anion of at least one mono- or polybasic,            inorganic or organic, natural or synthetic acid.        -   The quaternized nitrogen compound may be derived either from            a single epoxide of the formula I or a mixture of a            plurality of different epoxides of the formula I.

-   2. The fuel composition or lubricant composition according to    embodiment 1, wherein the reaction product comprises at least one    compound of the general formula IV

-   -   in which    -   the R₁, R₂, R₃, R₄, R_(a), R_(b), R_(c) and A radicals are each        as defined above.

-   3. The fuel composition or lubricant composition according to either    of embodiments 1 and 2, wherein the amine of the general formula II    is selected from tri-C₁-C₂₄- or tri-C₄-C₁₂-alkylamines or compounds    of the general formula II in which one of the R_(a), R_(b) and R_(c)    radicals is a C₁-C₄-alkyl radical and the two other radicals,    together with the nitrogen atom to which they are bonded, form a 5-    or 6-membered heterocyclic saturated or unsaturated ring which may    optionally bear at least one further ring heteroatom such as O, S or    N.

-   4. The fuel composition or lubricant composition according to any of    the preceding embodiments, wherein the compound of the general    formula I is a polyalkylene epoxide which is obtained by epoxidizing    a polyalkene, especially poly-(C₂-C₆)-alkene, having a    number-average molecular weight (M_(n)) of 85 to 20 000, for example    113 to 10 000, or 200 to 10 000 or 350 to 5000, for example 350 to    3000, 500 to 2500, 700 to 2500, or 800 to 1500.

-   5. The fuel composition or lubricant composition according to any of    embodiments 1 to 3, wherein the long-chain hydrocarbyl radical in    the compounds of the general formula I is a straight-chain or    branched aliphatic hydrocarbyl radical having 8 to 40, especially 10    to 20, 10 to 16 or 10 to 14 connected carbon atoms. Examples include    C₁₂-C₁₆-alkyl epoxides. Especially suitable compounds are those    which bear terminal epoxide groups, i.e. two adjacent carbon atoms    at the chain end (omega position) or in the omega-1 or omega-2    position bear the epoxide group.

-   6. The fuel composition or lubricant composition according to    embodiment 4, wherein the polyalkylene is a polyisobutene having a    proportion of vinylidene double bonds of greater than 70 mol %,    especially greater than 80 mol % or greater than 85 mol %.

-   7. The fuel composition or lubricant composition according to any of    the preceding embodiments, selected from diesel fuels, biodiesel    fuels, gasoline fuels, and alkanol-containing gasoline fuels.

-   8. A quaternized nitrogen compound comprising a reaction product as    defined in any of embodiments 1 to 5, especially a compound of the    formula IV.

-   9. A quaternized nitrogen compound of the above general formula IV.

-   10. A process for preparing a quaternized nitrogen compound    according to embodiment 7 or 8,    -   comprising the reaction of at least one hydrocarbyl epoxide of        the general formula I

-   -   -   in which        -   at least one of the R₁ and R₂ radicals is a straight-chain            or branched, saturated or unsaturated, long-chain            hydrocarbyl radical, e.g. polyalkylene radical, and the            other of the two radicals is optionally H or a short-chain            hydrocarbyl radical (especially C₁-C₄ alkyl); and        -   the R₃ and R₄ radicals are the same or different and are            each H or a short-chain hydrocarbyl radical (especially            C₁-C₄ alkyl);

with at least one tertiary amine of the general formula II

R_(a)R_(b)R_(c)N  (II)

-   -   -   in which        -   R_(a), R_(b) and R_(c) are each independently a            straight-chain or branched, saturated or unsaturated,            optionally substituted hydrocarbyl radical, especially            short-chain hydrocarbyl radical, or alkyl or alkenyl,            especially C₁-C₂₄-alkyl or C₂-C₂₄-alkenyl, or two of the            R_(a), R_(b) and R_(c) radicals, together with the nitrogen            atom to which they are bonded, form an optionally            substituted heterocyclic ring, especially 5- to 7-membered,            saturated or unsaturated, nonaromatic or aromatic            heterocyclic ring, which may optionally bear at least one            further ring heteroatom such as O, S or N;

    -   and in the presence of an acid of the formula III

H⁺A⁻  (III)

-   -   -   in which        -   A⁻ is the anion of at least one mono- or polybasic,            inorganic or organic, natural or synthetic acid.

-   11. The process according to embodiment 10, wherein the reaction    product comprises at least one compound of the general formula IV

-   -   in which    -   the R₁, R₂, R₃, R₄, R_(a), R_(b), R_(c) and A radicals are each        as defined above.

-   12. The process according to either of embodiments 10 and 11,    wherein the amine of the general formula II is selected from    tri-C₁-C₂₄- or tri-C₄-C₁₂-alkylamines or compounds of the general    formula II in which one of the R_(a), R_(b) and R_(c) radicals is a    C₁-C₄-alkyl radical and the two other radicals, together with the    nitrogen atom to which they are bonded, form a 5- or 6-membered    heterocyclic saturated or unsaturated ring which may optionally bear    at least one further ring heteroatom such as O, S or N.

-   13. The process according to any of the preceding embodiments,    wherein the compound of the general formula I is a polyalkylene    epoxide which is obtained by epoxidizing a polyalkene, especially    poly-(C₂-C₆)-alkene, having a number-average molecular weight    (M_(n)) of 85 to 20 000, for example 113 to 10 000, or 200 to 10 000    or 350 to 5000, for example 350 to 3000, 500 to 2500, 700 to 2500,    or 800 to 1500.

-   14. The process according to embodiment 13, wherein the polyalkylene    is a polyisobutene having a proportion of vinylidene double bonds of    greater than 70 mol %, especially greater than 80 mol % or greater    than 85 mol %.

-   15. The use of a quaternized nitrogen compound according to claim 8    or 9 or prepared according to any of embodiments 10 to 14 as a fuel    additive or lubricant additive.

-   16. The use according to embodiment 15 as an additive for reducing    the fuel consumption of direct injection diesel engines, especially    of diesel engines with common rail injection systems, and/or for    minimizing power loss in direct injection diesel engines, especially    in diesel engines with common rail injection systems, determined as    described in general terms in the experimental section (KC power    loss or DU power loss or DU,CU power loss).

-   17. The use according to embodiment 16 as a gasoline fuel additive    for reducing deposits in the intake system of a gasoline engine,    such as, more particularly, DISI and PFI (port fuel injector)    engines.

-   18. The use according to embodiment 17 as a diesel fuel additive for    reducing and/or preventing deposits in the intake systems, such as    especially the internal diesel injector deposits (IDIDs), and/or    valve sticking in direct injection diesel engines, especially in    common rail injection systems, each determined as described in    general terms in the experimental section (XUD-9 or IDIDI).

-   19. An additive concentrate comprising, in combination with further    diesel fuel additives or gasoline fuel additives or lubricant    additives, at least one quaternized nitrogen compound as defined in    embodiment 8 or 9 or prepared according to any of embodiments 10 to    14.

A2) General Definitions

In the absence of statements to the contrary, the following generalconditions apply:

“Hydrocarbyl” can be interpreted widely and comprises both long-chainand short-chain, cyclic and acyclic, straight-chain and branched,saturated and unsaturated, aliphatic, cycloaliphatic and aromatic (e.g.aryl), especially aliphatic, hydrocarbyl radicals having 1 to 50 carbonatoms, which may optionally additionally comprise heteroatoms, forexample O, N, NH, S, in the chain thereof.

“Long-chain” hydrocarbyl radicals are straight-chain or branchedhydrocarbyl radicals and have 7 to 50 or 8 to 40 or 10 to 20 carbonatoms, which may optionally additionally comprise heteroatoms, forexample O, N, NH, S, in the chain thereof. In a particular embodiment,no heteroatoms are present. In addition, the radicals may be mono- orpolyunsaturated and have one or more noncumulated, for example 1 to 5,such as 1, 2 or 3, C—C double bonds or C—C triple bonds, especially 1, 2or 3 double bonds. They may be of natural or synthetic origin. They mayalso have a number-average molecular weight (M_(n)) of 85 to 20 000, forexample 113 to 10 000, or 200 to 10 000 or 350 to 5000, for example 350to 3000, 500 to 2500, 700 to 2500, or 800 to 1500. In that case, theyare more particularly formed essentially from C₂₋₆, especially C₂₋₄,monomer units such as ethylene, propylene, n- or isobutylene or mixturesthereof, where the different monomers may be copolymerized in randomdistribution or as blocks. Such long-chain hydrocarbyl radicals are alsoreferred to as polyalkylene radicals or poly-C₂₋₆- or poly-C₂₋₄-alkyleneradicals. Suitable long-chain hydrocarbyl radicals and the preparationthereof are also described, for example, in WO 2006/135881 and theliterature cited therein.

Examples of particularly useful polyalkylene radicals are polyisobutenylradicals derived from what are called “high-reactivity” polyisobuteneswhich feature a high content of terminal double bonds. Terminal doublebonds are alpha-olefinic double bonds of the formula V

which are also referred to collectively as vinylidene double bonds.Suitable high-reactivity polyisobutenes are, for example, polyisobuteneswhich have a proportion of vinylidene double bonds of greater than 70mol %, especially greater than 80 mol % or greater than 85 mol %.Preference is given especially to polyisobutenes which have homogeneouspolymer skeletons. Homogeneous polymer skeletons are possessedespecially by those polyisobutenes formed from isobutene units to anextent of at least 85% by weight, preferably to an extent of at least90% by weight and more preferably to an extent of at least 95% byweight. Such high-reactivity polyisobutenes preferably have anumber-average molecular weight within the abovementioned range. Inaddition, the high-reactivity polyisobutenes may have a polydispersityin the range from 1.05 to 7, especially of about 1.1 to 2.5, for exampleof less than 1.9 or less than 1.5. Polydispersity is understood to meanthe quotient of weight-average molecular weight Mw divided by thenumber-average molecular weight Mn.

Particularly suitable high-reactivity polyisobutenes are, for example,the Glissopal brands from BASF SE, especially Glissopal 1000 (Mn=1000),Glissopal V 33 (Mn=550) and Glissopal 2300 (Mn=2300), and mixturesthereof. Other number-average molecular weights can be established in amanner known in principle by mixing polyisobutenes of differentnumber-average molecular weights or by extractive enrichment ofpolyisobutenes of particular molecular weight ranges.

“Short-chain hydrocarbyl” or “low molecular weight hydrocarbyl”represents especially straight-chain or branched C₁-C₇-alkyl orC₂-C₇-alkenyl, optionally interrupted by one or more, for example 2, 3or 4, heteroatom groups such as —O— or —NH—, or optionally mono- orpolysubstituted, for example di-, tri- or tetrasubstituted.

“Hydrocarbylene” represents straight-chain or singly or multiplybranched bridge groups having 1 to 10 carbon atoms, optionallyinterrupted by one or more, for example 2, 3 or 4, heteroatom groupssuch as —O— or —NH—, or optionally mono- or polysubstituted, for exampledi-, tri- or tetrasubstituted.

“Alkyl” or “lower alkyl” represents especially saturated, straight-chainor branched hydrocarbyl radicals having 1 to 4, 1 to 5, 1 to 6, 1 to 7,1 to 10, 1 to 16 or 1 to 24 carbon atoms, for example methyl, ethyl,n-propyl, 1-methylethyl, n-butyl, 1-methylpropyl, 2-methylpropyl,1,1-dimethylethyl, n-pentyl, 1-methylbutyl, 2-methylbutyl,3-methylbutyl, 2,2-dimethylpropyl, 1-ethylpropyl, n-hexyl,1,1-dimethylpropyl, 1,2-dimethylpropyl, 1-methylpentyl, 2-methylpentyl,3-methylpentyl, 4-methylpentyl, 1,1-dimethylbutyl, 1,2-dimethylbutyl,1,3-dimethylbutyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl,3,3-dimethylbutyl, 1-ethylbutyl, 2-ethylbutyl, 1,1,2-trimethylpropyl,1,2,2-trimethylpropyl, 1-ethyl-1-methylpropyl and1-ethyl-2-methylpropyl; and also n-heptyl, n-octyl, n-nonyl, n-decyl,n-undecyl, n-tridecyl, n-tetradecyl, n-pentadecyl and n-hexadecyl,octadecyl, docosanyl, and the singly or multiply branched analogsthereof. “Lower alkyl” represents especially radicals having 1 to 4, 1to 5, 1 to 6, or 1 to 7 carbon atoms.

“Hydroxyalkyl” represents especially the mono- orpoly-hydroxy-substituted, especially mono-hydroxy-substituted, analogsof above alkyl or lower alkyl groups.

“Alkenyl” represents mono- or polyunsaturated, especiallymonounsaturated, straight-chain or branched hydrocarbyl radicals having2 to 4, 2 to 6, 2 to 7, 2 to 10, 2 to 16 or 2 to 24 carbon atoms and adouble bond in any position, for example C₂-C₆-alkenyl such as ethenyl,1-propenyl, 2-propenyl, 1-methylethenyl, 1-butenyl, 2-butenyl,3-butenyl, 1-methyl-1-propenyl, 2-methyl-1-propenyl,1-methyl-2-propenyl, 2-methyl-2-propenyl, 1-pentenyl, 2-pentenyl,3-pentenyl, 4-pentenyl, 1-methyl-1-butenyl, 2-methyl-1-butenyl,3-methyl-1-butenyl, 1-methyl-2-butenyl, 2-methyl-2-butenyl,3-methyl-2-butenyl, 1-methyl-3-butenyl, 2-methyl-3-butenyl,3-methyl-3-butenyl, 1,1-dimethyl-2-propenyl, 1,2-dimethyl-1-propenyl,1,2-dimethyl-2-propenyl, 1-ethyl-1-propenyl, 1-ethyl-2-propenyl,1-hexenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl, 5-hexenyl,1-methyl-1-pentenyl, 2-methyl-1-pentenyl, 3-methyl-1-pentenyl,4-methyl-1-pentenyl, 1-methyl-2-pentenyl, 2-methyl-2-pentenyl,3-methyl-2-pentenyl, 4-methyl-2-pentenyl, 1-methyl-3-pentenyl,2-methyl-3-pentenyl, 3-methyl-3-pentenyl, 4-methyl-3-pentenyl,1-methyl-4-pentenyl, 2-methyl-4-pentenyl, 3-methyl-4-pentenyl,4-methyl-4-pentenyl, 1,1-dimethyl-2-butenyl, 1,1-dimethyl-3-butenyl,1,2-dimethyl-1-butenyl, 1,2-dimethyl-2-butenyl, 1,2-dimethyl-3-butenyl,1,3-dimethyl-1-butenyl, 1,3-dimethyl-2-butenyl, 1,3-dimethyl-3-butenyl,2,2-dimethyl-3-butenyl, 2,3-dimethyl-1-butenyl, 2,3-dimethyl-2-butenyl,2,3-dimethyl-3-butenyl, 3,3-dimethyl-1-butenyl, 3,3-dimethyl-2-butenyl,1-ethyl-1-butenyl, 1-ethyl-2-butenyl, 1-ethyl-3-butenyl,2-ethyl-1-butenyl, 2-ethyl-2-butenyl, 2-ethyl-3-butenyl,1,1,2-trimethyl-2-propenyl, 1-ethyl-1-methyl-2-propenyl,1-ethyl-2-methyl-1-propenyl and 1-ethyl-2-methyl-2-propenyl, and also,where unspecified, the monounsaturated analogs of the above alkylradicals. “Lower alkenyl” represents especially radicals having 2 to 4,2 to 5, 2 to 6, or 2 to 7 carbon atoms.

“Alkylene” represents straight-chain or singly or multiply branchedhydrocarbyl bridge groups having 1 to 10 or 2 to 6 carbon atoms, forexample C₁-C₇- or C₂-C₆-alkylene groups selected from —CH₂—, —(CH₂)₂—,—(CH₂)₃—, —CH₂—CH(CH₃)—, —CH(CH₃)—CH₂—, —(CH₂)₄—, —(CH₂)₂—CH(CH₃)—,—CH₂—CH(CH₃)—CH₂—, (CH₂)₄—, —(CH₂)₅—, —(CH₂)₆, —(CH₂)₇—,—CH(CH₃)—CH₂—CH₂—CH(CH₃)— or —CH(CH₃)—CH₂—CH₂—CH₂—CH(CH₃)— or C₁-C₄- orC₂-C₄-alkylene groups selected from —CH₂—, —(CH₂)₂—, —(CH₂)₃—,—CH₂—CH(CH₃)—, —CH(CH₃)—CH₂, —(CH₂)₄—, —(CH₂)₂—CH(CH₃)—,—CH₂—CH(CH₃)—CH₂—.

“Alkenylene” represents the mono- or polyunsaturated, especiallymonounsaturated, analogs of the above alkylene groups having 2 to 10carbon atoms, especially C₂-C₇-alkenylenes or C₂-C₄-alkenylene, such as—CH═CH—, —CH═CH—CH₂—,—CH₂—CH═CH—, —CH═CH—CH₂—CH₂—, —CH₂—CH═CH—CH₂—,—CH₂—CH₂—CH═CH—, —CH(CH₃)—CH═CH—, —CH₂—C(CH₃)═CH—.

“Cycloalkyl” represents carbocyclic radicals having 3 to 20 carbonatoms, for example C₃-C₁₂-cycloalkyl such as cyclopropyl, cyclobutyl,cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl,cyclodecyl, cycloundecyl and cyclododecyl; preference is given tocyclopentyl, cyclohexyl, cycloheptyl, and also to cyclopropylmethyl,cyclopropylethyl, cyclobutylmethyl, cyclobutylethyl, cyclopentylmethyl,cyclopentylethyl, cyclohexylmethyl, or C₃-C₇-cycloalkyl such ascyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl,cyclopropylmethyl, cyclopropylethyl, cyclobutylmethyl, cyclopentylethyl,cyclohexylmethyl, where the bond to the rest of the molecule may be viaany suitable carbon atom.

“Cycloaliphatic” radicals comprise especially the above cycloalkylradicals and the monounsaturated analogs (“cycloalkenyl”) thereof.

“Aryl” represents mono- or polycyclic, preferably mono- or bicyclic,optionally substituted aromatic radicals having 6 to 20, for example 6to 10, ring carbon atoms, for example phenyl, biphenyl, naphthyl such as1- or 2-naphthyl, tetrahydronaphthyl, fluorenyl, indenyl andphenanthrenyl. These aryl radicals may optionally bear 1, 2, 3, 4, 5 or6 identical or different substituents.

“Aralkyl” represents the mono- or poly-aryl-substituted analogs of abovealkyl or lower alkyl groups.

“Substituents” for radicals specified herein are especially, unlessstated otherwise, selected from keto groups, —COOH, —COO-alkyl, —OH,—SH, —CN, amino, —NO₂, alkyl, or alkenyl groups.

“Mn” represents the number-average molecular weight and is determined ina conventional manner; more particularly, such statements relate to Mnvalues determined, for example, by gel permeation chromatography;

especially determined by relative methods, such as gel permeationchromatography with THF as eluent and polystyrene standards, or absolutemethods such as vapor phase osmometry using toluene as solvent.

“Mw” represents the weight-average molecular weight and is determined ina conventional manner; more particularly, such figures relate to Mwvalues determined by relative methods, such as gel permeationchromatography with THF as eluent and polystyrene standards, or absolutemethods such as light scattering.

The “degree of polymerization” usually refers to the numerical meandegree of polymerization (determination method: gel permeationchromatography with THF as eluent and polystyrene standards; or GC-MScoupling).

A3) Hydrocarbyl Epoxides of the Formula (I)

Hydrocarbyl epoxides of the above formula I are compounds known per se(for example described in WO 2007/025700 or EP-A-1 422 246) or arepreparable in a manner known per se (cf., for example, Sienel, G.,Rieth, R. and Rowbottom, K. T. 2000. Epoxides. Ullmann's Encyclopedia ofIndustrial Chemistry).

Examples of suitable starting materials for epoxide preparation are inprinciple all compounds from the compound class of the polyalkenes,which is known per se, as described, for example, in Koch, H., Mawer, R.L. and Immel, W. 2011. Polybutenes. Ullmann's Encyclopedia of IndustrialChemistry, James L. White, Dongman Choi. 2004. Polyolefins: Processing,Structure Development, and Properties, Hanser.

More particularly, nonlimiting examples are what are called“high-reactivity” polyisobutenes which feature a high content ofterminal double bonds of the above formula V. Explicit reference is madehere once again to the above disclosure of high-reactivitypolyisobutenes.

The preparation of useful epoxides is illustrated by way of example bythe description of the preparation of a polybutene epoxide whichfollows.

To a solution of a polyisobutene in an apolar solvent, for examplen-heptane, are added, at room temperature, formic acid andmethyltrioctylammonium chloride (as described, for example, in WO2007/025700). The reaction mixture is heated, for example to atemperature in the range from 50 to 90° C., for example about 75° C.,and hydrogen peroxide solution is slowly added dropwise, while thepreset temperature is maintained. The reaction mixture is subsequentlystirred at the same temperature over a suitable period, for example 1 to36 hours, for instance 10 h, and cooled to room temperature, and thephases are separated. The organic phase is washed, for examplesuccessively with aqueous NaHSO₃ solution, saturated NaHCO₃ solution andwater. The organic phase is dried over Na₂SO₄ and the solvent isremoved.

A4) Tertiary Amines of the Formula (II)

Tertiary amines of the formula (II) are likewise compounds known per se,from the group of the aliphatic or aromatic amines. Examples include:

a) Noncyclic Tertiary Amines Such as:

amines of the general formula II in which the R_(a), R_(b) and R_(c)radicals are each independently C₁-C₂₄-alkyl such as methyl, ethyl,n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl,isopentyl, n-hexyl, isohexyl, or C₃- to C₁₂-cycloalkyl such ascyclopentyl, cyclohexyl and cycloheptyl, hydroxyalkyl such ashydroxy-C₁-C₂₄-alkyl, for example the mono-hydroxy-substituted analogsof the above alkyl or cycloalkyl groups; or aralkyl, for examplearyl-substituted C₁-C₄-alkyl radicals, for example benzyl. Nonlimitingexamples thereof are: trimethylamine, triethylamine, tripropylamine,dimethylethylamine, methyldiethylamine, ethyldipropylamine,methyldipropylamine, dimethylpropylamine, ethyldipropylamine,diethylpropylamine, tri-(n-butyl)amine, diisopropylethylamine,tripentylamine, trihexylamine, tricyclohexylamine,ethyldicyclohexylamine, N,N-dimethylbenzylamine,N,N-dimethylcyclohexylamine, N,N-dimethylethanolamine,N,N-diethylethanolamine, N,N-dimethylethylamine,N,N-dimethylpropylamine, N,N-dimethylisopropylamine,N-ethyldiisopropylamine, tris(2-ethylhexyl)amine,N,N,N′,N′-tetramethyl-1,6-hexanediamine,N,N,N′,N′-tetramethyl-1,3-propanediamine, triethanolamine,triisopropanolamine, N,N-dibutylethanolamine, N-methyldiethanolamine,N,N-dimethylisopropanolamine, N,N-di-(2-hydroxyethyl)aniline.

b) Cyclic Tertiary Amines Such as:

isopropyldimethylamine, N-methylpyrrolidone, N-methylimidazole,N-methylmorpholine, N-methylpiperidine, N-ethylpiperidine,N-ethylpyrrolidine, N-propylazepine, N-ethylmorpholine,N,N′-dimethylpiperazine.

4-aminopyridines in which the hydrogen atoms of the amino group havebeen replaced by R_(a), R_(b) or R_(c) radicals as defined above.Examples are N,N-dimethyl-4-aminopyridine, N,N-diethyl-4-aminopyridine,4-morpholinopyridine or 4-piperazinopyridine.

N-substituted imidazoles where the substituent is a C₁-C₂₄- orC₁-C₈-alkyl radical, for example N-methyl-, N-ethyl- orN-propylimidazole.

A5) Preparation of Inventive Quaternized Additives of the Formula (IV)a) Quaternization

The quaternization is performed in a manner known per se.

To perform the quaternization, the tertiary amine (II) is admixed withat least one epoxide compound of the above formula (I), especially inthe stoichiometric amounts required to achieve the desiredquaternization.

If required, the reactants can be dissolved in a suitable organicsolvent, especially alcoholic solvent, for example methanol or ethanol.

The reaction is additionally effected in the presence of stoichiometricamounts of an inorganic or especially organic acid of the above formula(III).

More particularly, organic carboxylic acids are used for this purpose,especially saturated or unsaturated, aliphatic or aromatic C₁-C₂₀carboxylic acids, for example C₁-C₄ monocarboxylic acid, formic acid,acetic acid, propionic acid, or aromatic carboxylic acids, such assalicylic acid and benzoic acid, or fatty acids. Suitable fatty acidsare straight-chain or branched, mono- or polyunsaturated, optionallysubstituted C₆-C₃₀-monocarboxylic acids. Examples of saturatedunbranched fatty acids are caproic acid, enanthic acid, caprylic acid,pelargonic acid, capric acid, undecanoic acid, lauric acid, tridecanoicacid, myristic acid, pentadecanoic acid, palmitic acid, margaric acid,stearic acid, nonadecanoic acid, arachic acid, behenic acid, lignocericacid, cerotic acid and melissic acid. Examples of monounsaturated fattyacids are palmitoleic acid, oleic acid and erucic acid. Examples ofdiunsaturated fatty acids are sorbic acid and linoleic acid. Examples oftriunsaturated fatty acids are linolenic acid and eleostearic acid.Examples of tetra- and polyunsaturated fatty acids are arachidonic acid,clupanodonic acid and docosahexaenoic acid. Examples of substitutedfatty acids are ricinoleic acid ((R)-12-hydroxy-(Z)-9-octadecenoicacid). Further suitable fatty acids are naturally occurring fatty acidssuch as gondoic acid and nervonic acid. If double bonds are present inthe fatty acids, they may be present either in cis or in trans form. Thesubstituents are preferably selected from hydroxyl and lower alkylgroups, for example methyl and ethyl groups. In addition, keto groups orepoxy groups, as, for example, in vernolic acid, may be present in thehydrocarbyl radical. Further functional groups are cyclopropane,cyclopropene and cyclopentene rings which can be formed by bridging oftwo adjacent carbon atoms in the hydrocarbyl radical of the fatty acid(cf. malvalic acid and chaulmoogric acid). Particular mention shouldalso be made of tall oil fatty acids.

Typical working temperatures here are in the range from 50 to 200° C.,for example 90 to 160° C. or 100 to 140° C. The reaction time may be inthe region of a few minutes or a few hours, for example about 10 minutesup to about 24 hours. The reaction can be effected at a pressure ofabout 1 to 20 bar, for example 1 to 10 bar, but especially in anautoclave at about standard pressure.

The reaction is additionally effected especially under inert gas, forexample nitrogen.

b) Workup of the Reaction Mixture

The reaction end product thus formed can theoretically be purifiedfurther, or the solvent can be removed. Optionally, excess reagent orvolatile constituents of the reaction mixture can be removed. Furtherpurification, for example by removal of nonquaternized constituents, isnot absolutely necessary, and so the reaction product may be usable asan additive merely after removal of volatile constituents, optionallyafter blending with further additive components (see below).

B) Further Additive Components

The fuel additized with the inventive quaternized additive is a gasolinefuel or especially a middle distillate fuel, in particular a dieselfuel.

The fuel may comprise further customary additives to improve efficacyand/or suppress wear.

In the case of diesel fuels, these are primarily customary detergentadditives, carrier oils, cold flow improvers, lubricity improvers,corrosion inhibitors, demulsifiers, dehazers, antifoams, cetane numberimprovers, combustion improvers, antioxidants or stabilizers, antistats,metallocenes, metal deactivators, dyes and/or solvents.

In the case of gasoline fuels, these are in particular lubricityimprovers (friction modifiers), corrosion inhibitors, demulsifiers,dehazers, antifoams, combustion improvers, antioxidants or stabilizers,antistats, metallocenes, metal deactivators, dyes and/or solvents.

Typical examples of suitable coadditives are listed in the followingsection:

B1) Detergent Additives

The customary detergent additives are preferably amphiphilic substanceswhich possess at least one hydrophobic hydrocarbyl radical with anumber-average molecular weight (M_(n)) of 85 to 20 000 and at least onepolar moiety selected from:

-   (Da) mono- or polyamino groups having up to 6 nitrogen atoms, at    least one nitrogen atom having basic properties;-   (Db) nitro groups, optionally in combination with hydroxyl groups;-   (Dc) hydroxyl groups in combination with mono- or polyamino groups,    at least one nitrogen atom having basic properties;-   (Dd) carboxyl groups or the alkali metal or alkaline earth metal    salts thereof;-   (De) sulfonic acid groups or the alkali metal or alkaline earth    metal salts thereof;-   (Df) polyoxy-C₂- to C₄-alkylene moieties terminated by hydroxyl    groups, mono- or polyamino groups, at least one nitrogen atom having    basic properties, or by carbamate groups;-   (Dg) carboxylic ester groups;-   (Dh) moieties derived from succinic anhydride and having hydroxyl    and/or amino and/or amido and/or imido groups; and/or-   (Di) moieties obtained by Mannich reaction of substituted phenols    with aldehydes and mono- or polyamines.

The hydrophobic hydrocarbon radical in the above detergent additives,which ensures the adequate solubility in the fuel, has a number-averagemolecular weight (M_(n)) of 85 to 20 000, preferably of 113 to 10 000,more preferably of 300 to 5000, even more preferably of 300 to 3000,even more especially preferably of 500 to 2500 and especially of 700 to2500, in particular of 800 to 1500. Useful typical hydrophobichydrocarbyl radicals are especially polypropenyl, polybutenyl andpolyisobutenyl radicals with a number-average molecular weight M_(n) ofpreferably in each case 300 to 5000, more preferably 300 to 3000, evenmore preferably 500 to 2500, even more especially preferably 700 to 2500and especially 800 to 1500 into consideration.

Examples of the above groups of detergent additives include thefollowing:

Additives comprising mono- or polyamino groups (Da) are preferablypolyalkenemono- or polyalkenepolyamines based on polypropene or onhigh-reactivity (i.e. having predominantly terminal double bonds) orconventional (i.e. having predominantly internal double bonds)polybutene or polyisobutene having M_(n)=300 to 5000, more preferably500 to 2500 and especially 700 to 2500. Such additives based onhigh-reactivity polyisobutene, which can be prepared from thepolyisobutene which may comprise up to 20% by weight of n-butene unitsby hydroformylation and reductive amination with ammonia, monoamines orpolyamines such as dimethylaminopropylamine, ethylenediamine,diethylenetriamine, triethylenetetramine or tetraethylenepentamine, areknown especially from EP-A 244 616. When polybutene or polyisobutenehaving predominantly internal double bonds (usually in the β and γpositions) are used as starting materials in the preparation of theadditives, a possible preparative route is by chlorination andsubsequent amination or by oxidation of the double bond with air orozone to give the carbonyl or carboxyl compound and subsequent aminationunder reductive (hydrogenating) conditions. The amines used here for theamination may be, for example, ammonia, monoamines or the abovementionedpolyamines. Corresponding additives based on polypropene are describedmore particularly in WO-A 94/24231.

Further particular additives comprising monoamino groups (Da) are thehydrogenation products of the reaction products of polyisobutenes havingan average degree of polymerization P=5 to 100 with nitrogen oxides ormixtures of nitrogen oxides and oxygen, as described more particularlyin WO-A 97/03946.

Further particular additives comprising monoamino groups (Da) are thecompounds obtainable from polyisobutene epoxides by reaction with aminesand subsequent dehydration and reduction of the amino alcohols, asdescribed more particularly in DE-A 196 20 262.

Additives comprising nitro groups (Db), optionally in combination withhydroxyl groups, are preferably reaction products of polyisobuteneshaving an average degree of polymerization P=5 to 100 or 10 to 100 withnitrogen oxides or mixtures of nitrogen oxides and oxygen, as describedmore particularly in WO-A 96/03367 and in WO-A 96/03479. These reactionproducts are generally mixtures of pure nitropolyisobutenes (e.g.α,β-dinitropolyisobutene) and mixed hydroxynitropolyisobutenes (e.g.α-nitro-β-hydroxypolyisobutene).

Additives comprising hydroxyl groups in combination with mono- orpolyamino groups (Dc) are especially reaction products of polyisobuteneepoxides obtainable from polyisobutene having preferably predominantlyterminal double bonds and M_(n)=300 to 5000, with ammonia or mono- orpolyamines, as described more particularly in EP-A 476 485.

Additives comprising carboxyl groups or their alkali metal or alkalineearth metal salts (Dd) are preferably copolymers of C₂- to C₄₀-olefinswith maleic anhydride which have a total molar mass of 500 to 20 000 andsome or all of whose carboxyl groups have been converted to the alkalimetal or alkaline earth metal salts and any remainder of the carboxylgroups has been reacted with alcohols or amines. Such additives aredisclosed more particularly by EP-A 307 815. Such additives serve mainlyto prevent valve seat wear and can, as described in WO-A 87/01126,advantageously be used in combination with customary fuel detergentssuch as poly(iso)buteneamines or polyetheramines.

Additives comprising sulfonic acid groups or their alkali metal oralkaline earth metal salts (De) are preferably alkali metal or alkalineearth metal salts of an alkyl sulfosuccinate, as described moreparticularly in EP-A 639 632. Such additives serve mainly to preventvalve seat wear and can be used advantageously in combination withcustomary fuel detergents such as poly(iso)buteneamines orpolyetheramines.

Additives comprising polyoxy-C₂-C₄-alkylene moieties (Df) are preferablypolyethers or polyetheramines which are obtainable by reaction of C₂- toC₆₀-alkanols, C₆- to C₃₀-alkanediols, mono- or di-C₂- toC₃₀-alkylamines, C₁- to C₃₀-alkylcyclohexanols or C₁- toC₃₀-alkylphenols with 1 to 30 mol of ethylene oxide and/or propyleneoxide and/or butylene oxide per hydroxyl group or amino group and, inthe case of the polyetheramines, by subsequent reductive amination withammonia, monoamines or polyamines. Such products are described moreparticularly in EP-A 310 875, EP-A 356 725, EP-A 700 985 and U.S. Pat.No. 4,877,416. In the case of polyethers, such products also havecarrier oil properties. Typical examples thereof are tridecanolbutoxylates or isotridecanol butoxylates, isononylphenol butoxylates andalso polyisobutenol butoxylates and propoxylates, and also thecorresponding reaction products with ammonia.

Additives comprising carboxylic ester groups (Dg) are preferably estersof mono-, di- or tricarboxylic acids with long-chain alkanols orpolyols, especially those having a minimum viscosity of 2 mm²/s at 100°C., as described more particularly in DE-A 38 38 918. The mono-, di- ortricarboxylic acids used may be aliphatic or aromatic acids, andparticularly suitable ester alcohols or ester polyols are long-chainrepresentatives having, for example, 6 to 24 carbon atoms. Typicalrepresentatives of the esters are adipates, phthalates, isophthalates,terephthalates and trimellitates of isooctanol, of isononanol, ofisodecanol and of isotridecanol. Such products also satisfy carrier oilproperties.

Additives comprising moieties derived from succinic anhydride and havinghydroxyl and/or amino and/or amido and/or especially imido groups (Dh)are preferably corresponding derivatives of alkyl- oralkenyl-substituted succinic anhydride and especially the correspondingderivatives of polyisobutenylsuccinic anhydride which are obtainable byreacting conventional or high-reactivity polyisobutene havingM_(n)=preferably 300 to 5000, more preferably 300 to 3000, even morepreferably 500 to 2500, even more especially preferably 700 to 2500 andespecially 800 to 1500, with maleic anhydride by a thermal route in anene reaction or via the chlorinated polyisobutene. The moieties havinghydroxyl and/or amino and/or amido and/or imido groups are, for example,carboxylic acid groups, acid amides of monoamines, acid amides of di- orpolyamines which, in addition to the amide function, also have freeamine groups, succinic acid derivatives having an acid and an amidefunction, carboximides with monoamines, carboximides with di- orpolyamines which, in addition to the imide function, also have freeamine groups, or diimides which are formed by the reaction of di- orpolyamines with two succinic acid derivatives. In the presence of imidomoieties D(h), the further detergent additive in the context of thepresent invention is, however, used only up to a maximum of 100% of theweight of compounds with betaine structure. Such fuel additives arecommon knowledge and are described, for example, in documents (1) and(2). They are preferably the reaction products of alkyl- oralkenyl-substituted succinic acids or derivatives thereof with aminesand more preferably the reaction products of polyisobutenyl-substitutedsuccinic acids or derivatives thereof with amines. Of particularinterest in this context are reaction products with aliphatic polyamines(polyalkyleneimines) such as especially ethylenediamine,diethylenetriamine, triethylenetetramine, tetraethylenepentamine,pentaethylenehexamine and hexaethyleneheptamine, which have an imidestructure.

Additives comprising moieties (Di) obtained by Mannich reaction ofsubstituted phenols with aldehydes and mono- or polyamines arepreferably reaction products of polyisobutene-substituted phenols withformaldehyde and mono- or polyamines such as ethylenediamine,diethylenetriamine, triethylenetetramine, tetraethylenepentamine ordimethylaminopropylamine. The polyisobutenyl-substituted phenols mayoriginate from conventional or high-reactivity polyisobutene havingM_(n)=300 to 5000. Such “polyisobutene Mannich bases” are described moreparticularly in EP-A 831 141.

One or more of the detergent additives mentioned can be added to thefuel in such an amount that the dosage of these detergent additives ispreferably 25 to 2500 ppm by weight, especially 75 to 1500 ppm byweight, in particular 150 to 1000 ppm by weight.

B2) Carrier Oils

Carrier oils additionally used may be of mineral or synthetic nature.Suitable mineral carrier oils are fractions obtained in crude oilprocessing, such as brightstock or base oils having viscosities, forexample, from the SN 500-2000 class; but also aromatic hydrocarbons,paraffinic hydrocarbons and alkoxyalkanols. Likewise useful is afraction which is obtained in the refining of mineral oil and is knownas “hydrocrack oil” (vacuum distillate cut having a boiling range offrom about 360 to 500° C., obtainable from natural mineral oil which hasbeen catalytically hydrogenated under high pressure and isomerized andalso deparaffinized). Likewise suitable are mixtures of theabovementioned mineral carrier oils.

Examples of suitable synthetic carrier oils are polyolefins(polyalphaolefins or polyinternalolefins), (poly)esters,(poly)alkoxylates, polyethers, aliphatic polyetheramines,alkylphenol-started polyethers, alkylphenol-started polyetheramines andcarboxylic esters of long-chain alkanols.

Examples of suitable polyolefins are olefin polymers having M_(n)=400 to1800, in particular based on polybutene or polyisobutene (hydrogenatedor unhydrogenated).

Examples of suitable polyethers or polyetheramines are preferablycompounds comprising polyoxy-C₂- to C_(a)-alkylene moieties which areobtainable by reacting C₂- to C₆₀-alkanols, C₆- to C₃₀-alkanediols,mono- or di-C₂- to C₃₀-alkylamines, C₁- to C₃₀-alkylcyclohexanols or C₁-to C₃₀-alkylphenols with 1 to 30 mol of ethylene oxide and/or propyleneoxide and/or butylene oxide per hydroxyl group or amino group, and, inthe case of the polyetheramines, by subsequent reductive amination withammonia, monoamines or polyamines. Such products are described moreparticularly in EP-A 310 875, EP-A 356 725, EP-A 700 985 and U.S. Pat.No. 4,877,416. For example, the polyetheramines used may be poly-C₂- toC₆-alkylene oxide amines or functional derivatives thereof. Typicalexamples thereof are tridecanol butoxylates or isotridecanolbutoxylates, isononylphenol butoxylates and also polyisobutenolbutoxylates and propoxylates, and also the corresponding reactionproducts with ammonia.

Examples of carboxylic esters of long-chain alkanols are moreparticularly esters of mono-, di- or tricarboxylic acids with long-chainalkanols or polyols, as described more particularly in DE-A 38 38 918.The mono-, di- or tricarboxylic acids used may be aliphatic or aromaticacids; particularly suitable ester alcohols or ester polyols arelong-chain representatives having, for example, 6 to 24 carbon atoms.Typical representatives of the esters are adipates, phthalates,isophthalates, terephthalates and trimellitates of isooctanol,isononanol, isodecanol and isotridecanol, for example di(n- orisotridecyl) phthalate.

Further suitable carrier oil systems are described, for example, in DE-A38 26 608, DE-A 41 42 241, DE-A 43 09 074, EP-A 452 328 and EP-A 548617.

Examples of particularly suitable synthetic carrier oils arealcohol-started polyethers having about 5 to 35, preferably about 5 to30, more preferably 10 to 30 and especially 15 to 30 C₃- to C₆-alkyleneoxide units, for example propylene oxide, n-butylene oxide andisobutylene oxide units, or mixtures thereof, per alcohol molecule.Nonlimiting examples of suitable starter alcohols are long-chainalkanols or phenols substituted by long-chain alkyl in which thelong-chain alkyl radical is especially a straight-chain or branched C₆-to C₁₈-alkyl radical. Particular examples include tridecanol andnonylphenol. Particularly preferred alcohol-started polyethers are thereaction products (polyetherification products) of monohydric aliphaticC₆- to C₁₈-alcohols with C₃- to C₆-alkylene oxides. Examples ofmonohydric aliphatic C₆-C₁₈-alcohols are hexanol, heptanol, octanol,2-ethylhexanol, nonyl alcohol, decanol, 3-propylheptanol, undecanol,dodecanol, tridecanol, tetradecanol, pentadecanol, hexadecanol,octadecanol and the constitutional and positional isomers thereof. Thealcohols can be used either in the form of the pure isomers or in theform of technical grade mixtures. A particularly preferred alcohol istridecanol. Examples of C₃- to C₆-alkylene oxides are propylene oxide,such as 1,2-propylene oxide, butylene oxide, such as 1,2-butylene oxide,2,3-butylene oxide, isobutylene oxide or tetrahydrofuran, pentyleneoxide and hexylene oxide. Particular preference among these is given toC₃- to C₄-alkylene oxides, i.e. propylene oxide such as 1,2-propyleneoxide and butylene oxide such as 1,2-butylene oxide, 2,3-butylene oxideand isobutylene oxide. Especially butylene oxide is used.

Further suitable synthetic carrier oils are alkoxylated alkylphenols, asdescribed in DE-A 10 102 913.

Particular carrier oils are synthetic carrier oils, particularpreference being given to the above-described alcohol-startedpolyethers.

The carrier oil or the mixture of different carrier oils is added to thefuel in an amount of preferably 1 to 1000 ppm by weight, more preferablyof 10 to 500 ppm by weight and especially of 20 to 100 ppm by weight.

B3) Cold Flow Improvers

Suitable cold flow improvers are in principle all organic compoundswhich are capable of improving the flow performance of middle distillatefuels or diesel fuels under cold conditions. For the intended purpose,they must have sufficient oil solubility. More particularly, useful coldflow improvers for this purpose are the cold flow improvers (middledistillate flow improvers, MDFIs) typically used in the case of middledistillates of fossil origin, i.e. in the case of customary mineraldiesel fuels. However, it is also possible to use organic compoundswhich partly or predominantly have the properties of a wax antisettlingadditive (WASA) when used in customary diesel fuels. They can also actpartly or predominantly as nucleators. It is also possible to usemixtures of organic compounds effective as MDFIs and/or effective asWASAs and/or effective as nucleators.

The cold flow improver is typically selected from:

(K1) copolymers of a C₂- to C₄₀-olefin with at least one furtherethylenically unsaturated monomer;(K2) comb polymers;(K3) polyoxyalkylenes;(K4) polar nitrogen compounds;(K5) sulfocarboxylic acids or sulfonic acids or derivatives thereof; and(K6) poly(meth)acrylic esters.

It is possible to use either mixtures of different representatives fromone of the particular classes (K1) to (K6) or mixtures ofrepresentatives from different classes (K1) to (K6).

Suitable C₂- to C₄₀-olefin monomers for the copolymers of class (K1)are, for example, those having 2 to 20 and especially 2 to 10 carbonatoms, and 1 to 3 and preferably 1 or 2 carbon-carbon double bonds,especially having one carbon-carbon double bond. In the latter case, thecarbon-carbon double bond may be arranged either terminally (α-olefins)or internally. However, preference is given to α-olefins, particularpreference to α-olefins having 2 to 6 carbon atoms, for example propene,1-butene, 1-pentene, 1-hexene and in particular ethylene.

In the copolymers of class (K1), the at least one further ethylenicallyunsaturated monomer is preferably selected from alkenyl carboxylates,(meth)acrylic esters and further olefins.

When further olefins are also copolymerized, they are preferably higherin molecular weight than the abovementioned C₂- to C₄₀-olefin basemonomer. When, for example, the olefin base monomer used is ethylene orpropene, suitable further olefins are especially C₁₀- to C₄₀-α-olefins.Further olefins are in most cases only additionally copolymerized whenmonomers with carboxylic ester functions are also used.

Suitable (meth)acrylic esters are, for example, esters of (meth)acrylicacid with C₁- to C₂₀-alkanols, especially C₁- to C₁₀-alkanols, inparticular with methanol, ethanol, propanol, isopropanol, n-butanol,sec-butanol, isobutanol, tert-butanol, pentanol, hexanol, heptanol,octanol, 2-ethylhexanol, nonanol and decanol, and structural isomersthereof.

Suitable alkenyl carboxylates are, for example, C₂- to C₁₄-alkenylesters, for example the vinyl and propenyl esters, of carboxylic acidshaving 2 to 21 carbon atoms, whose hydrocarbyl radical may be linear orbranched. Among these, preference is given to the vinyl esters. Amongthe carboxylic acids with a branched hydrocarbyl radical, preference isgiven to those whose branch is in the α position to the carboxyl group,and the α-carbon atom is more preferably tertiary, i.e. the carboxylicacid is what is called a neocarboxylic acid. However, the hydrocarbylradical of the carboxylic acid is preferably linear.

Examples of suitable alkenyl carboxylates are vinyl acetate, vinylpropionate, vinyl butyrate, vinyl 2-ethylhexanoate, vinyl neopentanoate,vinyl hexanoate, vinyl neononanoate, vinyl neodecanoate and thecorresponding propenyl esters, preference being given to the vinylesters. A particularly preferred alkenyl carboxylate is vinyl acetate;typical copolymers of group (K1) resulting therefrom are ethylene-vinylacetate copolymers (“EVAs”), which are some of the most frequently used.

Ethylene-vinyl acetate copolymers usable particularly advantageously andthe preparation thereof are described in WO 99/29748.

Suitable copolymers of class (K1) are also those which comprise two ormore different alkenyl carboxylates in copolymerized form, which differin the alkenyl function and/or in the carboxylic acid group. Likewisesuitable are copolymers which, as well as the alkenyl carboxylate(s),comprise at least one olefin and/or at least one (meth)acrylic ester incopolymerized form.

Terpolymers of a C₂- to C₄₀-α-olefin, a C₁- to C₂₀-alkyl ester of anethylenically unsaturated monocarboxylic acid having 2 to 15 carbonatoms and a C₂- to C₁₄-alkenyl ester of a saturated monocarboxylic acidhaving 2 to 21 carbon atoms are also suitable as copolymers of class(K1). Terpolymers of this kind are described in WO 2005/054314. Atypical terpolymer of this kind is formed from ethylene, 2-ethylhexylacrylate and vinyl acetate.

The at least one or the further ethylenically unsaturated monomer(s) arecopolymerized in the copolymers of class (K1) in an amount of preferably1 to 50% by weight, especially 10 to 45% by weight and in particular 20to 40% by weight, based on the overall copolymer. The main proportion interms of weight of the monomer units in the copolymers of class (K1)therefore originates generally from the C₂ to C₄₀ base olefins.

The copolymers of class (K1) preferably have a number-average molecularweight M_(n) of 1000 to 20 000, more preferably of 1000 to 10 000 andespecially of 1000 to 8000.

Typical comb polymers of component (K2) are, for example, obtainable bythe copolymerization of maleic anhydride or fumaric acid with anotherethylenically unsaturated monomer, for example with an α-olefin or anunsaturated ester, such as vinyl acetate, and subsequent esterificationof the anhydride or acid function with an alcohol having at least 10carbon atoms. Further suitable comb polymers are copolymers of α-olefinsand esterified comonomers, for example esterified copolymers of styreneand maleic anhydride or esterified copolymers of styrene and fumaricacid. Suitable comb polymers may also be polyfumarates or polymaleates.Homo- and copolymers of vinyl ethers are also suitable comb polymers.Comb polymers suitable as components of class (K2) are, for example,also those described in WO 2004/035715 and in “Comb-Like Polymers.Structure and Properties”, N. A. Plate and V. P. Shibaev, J. Poly. Sci.Macromolecular Revs. 8, pages 117 to 253 (1974). Mixtures of combpolymers are also suitable.

Polyoxyalkylenes suitable as components of class (K3) are, for example,polyoxyalkylene esters, polyoxyalkylene ethers, mixed polyoxyalkyleneester/ethers and mixtures thereof. These polyoxyalkylene compoundspreferably comprise at least one linear alkyl group, preferably at leasttwo linear alkyl groups, each having 10 to 30 carbon atoms and apolyoxyalkylene group having a number-average molecular weight of up to5000. Such polyoxyalkylene compounds are described, for example, in EP-A061 895 and also in U.S. Pat. No. 4,491,455. Particular polyoxyalkylenecompounds are based on polyethylene glycols and polypropylene glycolshaving a number-average molecular weight of 100 to 5000. Additionallysuitable are polyoxyalkylene mono- and diesters of fatty acids having 10to 30 carbon atoms, such as stearic acid or behenic acid.

Polar nitrogen compounds suitable as components of class (K4) may beeither ionic or nonionic and preferably have at least one substituent,especially at least two substituents, in the form of a tertiary nitrogenatom of the general formula >NR⁷ in which R¹ is a C₈- to C₄₀-hydrocarbylradical. The nitrogen substituents may also be quaternized, i.e. be incationic form. An example of such nitrogen compounds is that of ammoniumsalts and/or amides which are obtainable by the reaction of at least oneamine substituted by at least one hydrocarbyl radical with a carboxylicacid having 1 to 4 carboxyl groups or with a suitable derivativethereof. The amines preferably comprise at least one linear C₈- toC₄₀-alkyl radical. Primary amines suitable for preparing the polarnitrogen compounds mentioned are, for example, octylamine, nonylamine,decylamine, undecylamine, dodecylamine, tetradecylamine and the higherlinear homologs; secondary amines suitable for this purpose are, forexample, dioctadecylamine and methylbehenylamine. Also suitable for thispurpose are amine mixtures, especially amine mixtures obtainable on theindustrial scale, such as fatty amines or hydrogenated tallamines, asdescribed, for example, in Ullmann's Encyclopedia of IndustrialChemistry, 6th Edition, “Amines, aliphatic” chapter. Acids suitable forthe reaction are, for example, cyclohexane-1,2-dicarboxylic acid,cyclohexene-1,2-dicarboxylic acid, cyclopentane-1,2-dicarboxylic acid,naphthalenedicarboxylic acid, phthalic acid, isophthalic acid,terephthalic acid, and succinic acids substituted by long-chainhydrocarbyl radicals.

More particularly, the component of class (K4) is an oil-solublereaction product of poly(C₂- to C₂₀-carboxylic acids) having at leastone tertiary amino group with primary or secondary amines. The poly(C₂-to C₂₀-carboxylic acids) which have at least one tertiary amino groupand form the basis of this reaction product comprise preferably at least3 carboxyl groups, especially 3 to 12 and in particular 3 to 5 carboxylgroups. The carboxylic acid units in the polycarboxylic acids havepreferably 2 to 10 carbon atoms, and are especially acetic acid units.The carboxylic acid units are suitably bonded to the polycarboxylicacids, usually via one or more carbon and/or nitrogen atoms. They arepreferably attached to tertiary nitrogen atoms which, in the case of aplurality of nitrogen atoms, are bonded via hydrocarbon chains.

The component of class (K4) is preferably an oil-soluble reactionproduct based on poly(C₂- to C₂₀-carboxylic acids) which have at leastone tertiary amino group and are of the general formula IIa or IIb

in which the variable A denotes a straight-chain or branched C₂- toC₆-alkylene group or the moiety of the formula III

and the variable B denotes a C₁- to C₁₉-alkylene group. The compounds ofthe general formulae IIa and IIb especially have the properties of aWASA.

Moreover, the preferred oil-soluble reaction product of component (K4),especially that of the general formula IIa or IIb, is an amide, anamide-ammonium salt or an ammonium salt in which no, one or morecarboxylic acid groups have been converted to amide groups.

Straight-chain or branched C₂- to C₆-alkylene groups of the variable Aare, for example, 1,1-ethylene, 1,2-propylene, 1,3-propylene,1,2-butylene, 1,3-butylene, 1,4-butylene, 2-methyl-1,3-propylene,1,5-pentylene, 2-methyl-1,4-butylene, 2,2-dimethyl-1,3-propylene,1,6-hexylene (hexamethylene) and especially 1,2-ethylene. The variable Acomprises preferably 2 to 4 and especially 2 or 3 carbon atoms.

C₁- to C₁₉-alkylene groups of the variable B are, for example,1,2-ethylene, 1,3-propylene, 1,4-butylene, hexamethylene, octamethylene,decamethylene, dodecamethylene, tetradecamethylene, hexadecamethylene,octadecamethylene, nonadecamethylene and especially methylene. Thevariable B comprises preferably 1 to 10 and especially 1 to 4 carbonatoms.

The primary and secondary amines as a reaction partner for thepolycarboxylic acids to form component (K4) are typically monoamines,especially aliphatic monoamines. These primary and secondary amines maybe selected from a multitude of amines which bear hydrocarbyl radicalswhich may optionally be bonded to one another.

These parent amines of the oil-soluble reaction products of component(K4) are usually secondary amines and have the general formula HN(R⁸)₂in which the two variables R⁸ are each independently straight-chain orbranched C₁₀- to C₃₀-alkyl radicals, especially C₁₄- to C₂₄-alkylradicals. These relatively long-chain alkyl radicals are preferablystraight-chain or only slightly branched. In general, the secondaryamines mentioned, with regard to their relatively long-chain alkylradicals, derive from naturally occurring fatty acids and fromderivatives thereof. The two R⁸ radicals are preferably the same.

The secondary amines mentioned may be bonded to the polycarboxylic acidsby means of amide structures or in the form of the ammonium salts; it isalso possible for only a portion to be present as amide structures andanother portion as ammonium salts. Preferably only few, if any, freeacid groups are present. The oil-soluble reaction products of component(K4) are preferably present completely in the form of the amidestructures.

Typical examples of such components (K4) are reaction products ofnitrilotriacetic acid, of ethylenediaminetetraacetic acid or ofpropylene-1,2-diaminetetraacetic acid with in each case 0.5 to 1.5 molper carboxyl group, especially 0.8 to 1.2 mol per carboxyl group, ofdioleylamine, dipalmitamine, dicocoamine, distearylamine, dibehenylamineor especially ditallamine. A particularly preferred component (K4) isthe reaction product of 1 mol of ethylenediaminetetraacetic acid and 4mol of hydrogenated ditallamine.

Further typical examples of component (K4) include theN,N-dialkylammonium salts of 2-N′,N′-dialkylamidobenzoates, for examplethe reaction product of 1 mol of phthalic anhydride and 2 mol ofditallamine, the latter being hydrogenated or unhydrogenated, and thereaction product of 1 mol of an alkenylspirobislactone with 2 mol of adialkylamine, for example ditallamine and/or tallamine, the latter twobeing hydrogenated or unhydrogenated.

Further typical structure types for the component of class (K4) arecyclic compounds with tertiary amino groups or condensates of long-chainprimary or secondary amines with carboxylic acid-containing polymers, asdescribed in WO 93/18115.

Sulfocarboxylic acids, sulfonic acids or derivatives thereof which aresuitable as cold flow improvers of the component of class (K5) are, forexample, the oil-soluble carboxamides and carboxylic esters ofortho-sulfobenzoic acid, in which the sulfonic acid function is presentas a sulfonate with alkyl-substituted ammonium cations, as described inEP-A 261 957.

Poly(meth)acrylic esters suitable as cold flow improvers of thecomponent of class (K6) are either homo- or copolymers of acrylic andmethacrylic esters. Preference is given to copolymers of at least twodifferent (meth)acrylic esters which differ with regard to theesterified alcohol. The copolymer optionally comprises another differentolefinically unsaturated monomer in copolymerized form. Theweight-average molecular weight of the polymer is preferably 50 000 to500 000. A particularly preferred polymer is a copolymer of methacrylicacid and methacrylic esters of saturated C₁₄- and C₁₅-alcohols, the acidgroups having been neutralized with hydrogenated tallamine. Suitablepoly(meth)acrylic esters are described, for example, in WO 00/44857.

The cold flow improver or the mixture of different cold flow improversis added to the middle distillate fuel or diesel fuel in a total amountof preferably 10 to 5000 ppm by weight, more preferably of 20 to 2000ppm by weight, even more preferably of 50 to 1000 ppm by weight andespecially of 100 to 700 ppm by weight, for example of 200 to 500 ppm byweight.

B4) Lubricity Improvers

Suitable lubricity improvers or friction modifiers are based typicallyon fatty acids or fatty acid esters. Typical examples are tall oil fattyacid, as described, for example, in WO 98/004656, and glycerylmonooleate. The reaction products, described in U.S. Pat. No. 6,743,266B2, of natural or synthetic oils, for example triglycerides, andalkanolamines are also suitable as such lubricity improvers.

B5) Corrosion Inhibitors

Suitable corrosion inhibitors are, for example, succinic esters, inparticular with polyols, fatty acid derivatives, for example oleicesters, oligomerized fatty acids, substituted ethanolamines, andproducts sold under the trade name RC 4801 (Rhein Chemie Mannheim,Germany) or HiTEC 536 (Ethyl Corporation).

B6) Demulsifiers

Suitable demulsifiers are, for example, the alkali metal or alkalineearth metal salts of alkyl-substituted phenol- and naphthalenesulfonatesand the alkali metal or alkaline earth metal salts of fatty acids, andalso neutral compounds such as alcohol alkoxylates, e.g. alcoholethoxylates, phenol alkoxylates, e.g. tert-butylphenol ethoxylate ortert-pentylphenol ethoxylate, fatty acids, alkylphenols, condensationproducts of ethylene oxide (EO) and propylene oxide (PO), for exampleincluding in the form of EO/PO block copolymers, polyethyleneimines orelse polysiloxanes.

B7) Dehazers

Suitable dehazers are, for example, alkoxylated phenol-formaldehydecondensates, for example the products available under the trade namesNALCO 7D07 (Nalco) and TOLAD 2683 (Petrolite).

B8) Antifoams

Suitable antifoams are, for example, polyether-modified polysiloxanes,for example the products available under the trade names TEGOPREN 5851(Goldschmidt), Q 25907 (Dow Corning) and RHODOSIL (Rhone Poulenc).

B9) Cetane Number Improvers

Suitable cetane number improvers are, for example, aliphatic nitratessuch as 2-ethylhexyl nitrate and cyclohexyl nitrate and peroxides suchas di-tert-butyl peroxide.

B10) Antioxidants

Suitable antioxidants are, for example, substituted phenols, such as2,6-di-tert-butylphenol and 6-di-tert-butyl-3-methylphenol, and alsophenylenediamines such as N,N′-di-sec-butyl-p-phenylenediamine.

B11) Metal Deactivators

Suitable metal deactivators are, for example, salicylic acid derivativessuch as N,N′-disalicylidene-1,2-propanediamine.

B12) Solvents

Suitable solvents are, for example, nonpolar organic solvents such asaromatic and aliphatic hydrocarbons, for example toluene, xylenes, whitespirit and products sold under the trade names SHELLSOL (RoyalDutch/Shell Group) and EXXSOL (ExxonMobil), and also polar organicsolvents, for example, alcohols such as 2-ethylhexanol, decanol andisotridecanol. Such solvents are usually added to the diesel fueltogether with the aforementioned additives and coadditives, which theyare intended to dissolve or dilute for better handling.

C) Fuels

The inventive additive is outstandingly suitable as a fuel additive andcan be used in principle in any fuels. It brings about a whole series ofadvantageous effects in the operation of internal combustion engineswith fuels. Preference is given to using the inventive quaternizedadditive in middle distillate fuels, especially diesel fuels.

The present invention therefore also provides fuels, especially middledistillate fuels, with a content of the inventive quaternized additivewhich is effective as an additive for achieving advantageous effects inthe operation of internal combustion engines, for example of dieselengines, especially of direct injection diesel engines, in particular ofdiesel engines with common rail injection systems. This effectivecontent (dosage) in inventive fuels is generally 10 to 5000 ppm byweight, preferably 20 to 1500 ppm by weight, especially 25 to 1000 ppmby weight, in particular 30 to 750 ppm by weight, based in each case onthe total amount of fuel.

Middle distillate fuels such as diesel fuels or heating oils arepreferably mineral oil raffinates which typically have a boiling rangefrom 100 to 400° C. These are usually distillates having a 95% point upto 360° C. or even higher. These may also be what is called “ultra lowsulfur diesel” or “city diesel”, characterized by a 95% point of, forexample, not more than 345° C. and a sulfur content of not more than0.005% by weight or by a 95% point of, for example, 285° C. and a sulfurcontent of not more than 0.001% by weight. In addition to the mineralmiddle distillate fuels or diesel fuels obtainable by refining, thoseobtainable by coal gasification or gas liquefaction [“gas to liquid”(GTL) fuels] or by biomass liquefaction [“biomass to liquid” (BTL)fuels] are also suitable. Also suitable are mixtures of theaforementioned middle distillate fuels or diesel fuels with renewablefuels, such as biodiesel or bioethanol.

The qualities of the heating oils and diesel fuels are laid down indetail, for example, in DIN 51603 and EN 590 (cf. also Ullmann'sEncyclopedia of Industrial Chemistry, 5th edition, Volume A12, p. 617ff.).

In addition to the use thereof in the abovementioned middle distillatefuels of fossil, vegetable or animal origin, which are essentiallyhydrocarbon mixtures, the inventive quaternized additive can also beused in mixtures of such middle distillates with biofuel oils(biodiesel). Such mixtures are also encompassed by the term “middledistillate fuel” in the context of the present invention. They arecommercially available and usually comprise the biofuel oils in minoramounts, typically in amounts of 1 to 30% by weight, especially of 3 to10% by weight, based on the total amount of middle distillate of fossil,vegetable or animal origin and biofuel oil.

Biofuel oils are generally based on fatty acid esters, preferablyessentially on alkyl esters of fatty acids which derive from vegetableand/or animal oils and/or fats. Alkyl esters are typically understood tomean lower alkyl esters, especially C₁-C₄-alkyl esters, which areobtainable by transesterifying the glycerides which occur in vegetableand/or animal oils and/or fats, especially triglycerides, by means oflower alcohols, for example ethanol or in particular methanol (“FAME”).Typical lower alkyl esters based on vegetable and/or animal oils and/orfats, which find use as a biofuel oil or components thereof, are, forexample, sunflower methyl ester, palm oil methyl ester (“PME”), soya oilmethyl ester (“SME”) and especially rapeseed oil methyl ester (“RME”).

The middle distillate fuels or diesel fuels are more preferably thosehaving a low sulfur content, i.e. having a sulfur content of less than0.05% by weight, preferably of less than 0.02% by weight, moreparticularly of less than 0.005% by weight and especially of less than0.001% by weight of sulfur.

Useful gasoline fuels include all commercial gasoline fuel compositions.One typical representative which shall be mentioned here is theEurosuper base fuel to EN 228, which is customary on the market. Inaddition, gasoline fuel compositions of the specification according toWO 00/47698 are also possible fields of use for the present invention.

The inventive quaternized additive is especially suitable as a fueladditive in fuel compositions, especially in diesel fuels, forovercoming the problems outlined at the outset in direct injectiondiesel engines, in particular in those with common rail injectionsystems.

The invention is now illustrated in detail by the working examples whichfollow:

Experimental: Reagents Used:

Polyisobutene 1000: Glissopal® 1000 from BASF, Mn=1000Formic acid from BASF, CAS 64-18-6Methyltrioctylammonium chloride from Aldrich, 63393-96-4n-Heptane from Aldrich, CAS 142-82-5Methanol from Aldrich, CAS 67-56-1Acetic acid (99-100%) from Roth, CAS 64-19-7N-Methylpyrrolidine from BASF, CAS 120-94-51-Dodecene oxide from Aldrich, CAS 2855-19-81-Tetradecene oxide, CAS 3234-28-41-Hexadecene oxide, CAS 7320-37-8Isopropanol from Aldrich, CAS 67-63-0Trimethylamine NMe₃ (>99.5% (w/w)) from BASF, CAS 75-50-3Tall oil fatty acid: Kerokorr® LA 99 C from BASF, TAN 199 mg KOH/gN,N-Dimethylethanolamine from BASF, CAS 108-01-0Salicylic acid from Merck, CAS 69-72-7

A. General Test Methods

These methods form part of the general disclosure and are not limited tothe compounds specifically tested.

Engine Test 1. XUD9 Test—Determination of Flow Restriction

The procedure is according to the standard provisions of CEC F-23-1-01.

2. DW10 Test—Determination of Power Loss as a Result of InjectorDeposits in the Common Rail Diesel Engine 2.1. DW10-KC—Keep-Clean Test

The keep-clean test is based on CEC test procedure F-098-08 Issue 5.This is done using the same test setup and engine type (PEUGEOT DW10) asin the CEC procedure.

Change and Special Features:

In the tests, cleaned injectors were used. The cleaning time in theultrasound bath in water+10% Superdecontamine (Intersciences, Brussels)at 60° C. was 4 h.

Test Run Times:

The test run time was 12 h without shutdown phases. The one-hour testcycle from CEC F-098-08, shown in FIG. 1, was run through 12 times.

Performance Determination:

The initial power P0,KC [kW] is calculated from the measured torque atfull load 4000/min directly after the test has started and the enginehas run hot. The procedure is described in Issue 5 of the test procedure(CEC F-98-08). This is done using the same test setup and the PEUGEOTDW10 engine type.

The final performance (Pend,KC) is determined in the 12th cycle in stage12 (see table, FIG. 1). Here too, the operation point is full load4000/min. Pend,KC [kW] is calculated from the torque measured.

The power loss in the KC test is calculated as follows:

${Powerloss},{{{KC}\mspace{11mu}\lbrack\%\rbrack} = {\left( {1 - \frac{{Pend},{KC}}{{P\; 0},{KC}}} \right)*100}}$

2.2. DW10 Dirty-Up Clean-Up (DU-CU)

The DU-CU test is based on CEC test procedure F-098-08 Issue 5. Theprocedure is described in Issue 5 of the test procedure (CEC F-98-08).This is done using the same test setup and the PEUGEOT DW10 engine type.

The DU-CU test consists of two individual tests which are run insuccession. The first test serves to form deposits (DU), the second toremove the deposits (CU). After the DU, the power loss is determined.After the end of the DU run, the engine is not operated for at least 8hours and is cooled to ambient temperature. Thereafter, the CU fuel isused to start the CU without deinstalling and cleaning the injectors.The deposits and power loss ideally decline over the course of the CUtest.

Change and Special Features:

Cleaned injectors were installed in the engine prior to each DU test.The cleaning time in the ultrasound bath at 60° C., in water+10%Superdecontamine (Intersciences, Brussels), was 4 h.

Test Run Times:

The test run time was 12 h for the DU and 12 h for the CU. The enginewas operated in the DU and CU tests without shutdown phases.

The one-hour test cycle from CEC F-098-08, shown in FIG. 1, was runthrough 12 times in each case.

Performance Determination:

The initial power P0,du [kW] is calculated from the measured torque atfull load 4000/min directly after the test has started and the enginehas run hot. The procedure is likewise described in Issue 5 of the testprocedure.

The final performance (Pend,du) is determined in the 12th cycle in stage12 (see table above). Here too, the operation point is full load4000/min. Pend,du [kW] is calculated from the torque measured.

The power loss in the DU is calculated as follows:

${Powerloss},{{{du}\mspace{11mu}\lbrack\%\rbrack} = {\left( {1 - \frac{{Pend},{du}}{{P\; 0},{du}}} \right)*100}}$

Clean-Up

The initial power P0,cu [kW] is calculated from the measured torque atfull load 4000/min directly after the test has started and the enginehas run hot in the CU. The procedure is likewise described in Issue 5 ofthe test procedure.

The final performance (Pend,cu) is determined in the 12th cycle in stage12 (see table, FIG. 1). Here too, the operation point is full load4000/min. Pend,cu [kW] is calculated from the torque measured.

The power loss in the CU test is calculated as follows (negative numberfor the power loss in the cu test means an increase in performance)

${{{Powerloss}\left( {{DU},{CU}} \right)}\mspace{11mu}\lbrack\%\rbrack} = {\left( \frac{{Pend},{{du} - {pend}},{cu}}{{P\; 0},{du}} \right)*100}$

The fuel used was a commercial diesel fuel from Haltermann (RF-06-03).To artificially induce the formation of deposits at the injectors, 1 ppmby weight of zinc in the form of a zinc didodecanoate solution was addedthereto.

3. IDID Test—Determination of Additive Effect on Internal InjectorDeposits

The formation of deposits within the injector was characterized by thedeviations in the exhaust gas temperatures of the cylinders at thecylinder outlet on cold starting of the DW10 engine.

To promote the formation of deposits, 1 mg/I of sodium salt of anorganic acid, 20 mg/I of dodecenylsuccinic acid and 10 mg/I of waterwere added to the fuel.

The test is conducted as a dirty-up clean-up test (DU-CU).

DU-CU is based on CEC test procedure F-098-08 Issue 5.

The DU-CU test consists of two individual tests which are run insuccession. The first test serves to form deposits (DU), the second toremove the deposits (CU).

After the DU run, after a rest phase of at least eight hours, a coldstart of the engine is conducted, followed by idling for 10 minutes.

Thereafter, the CU fuel is used to start the CU without deinstalling andcleaning the injectors. After the CU run over 8 h, after a rest phase ofat least eight hours, a cold start of the engine is conducted, followedby idling for 10 minutes. The evaluation is effected by the comparisonof the temperature profiles for the individual cylinders after the coldstart in the du and CU runs.

The IDID test indicates the formation of internal deposits in theinjector. The characteristic used in this test is the exhaust gastemperature of the individual cylinders. In an injector system withoutIDIDs, the exhaust gas temperatures of the cylinders increasehomogeneously. In the presence of IDIDs, the exhaust gas temperatures ofthe individual cylinders do not increase homogeneously and deviate fromone another.

The temperature sensors are beyond the cylinder head outlet in theexhaust gas manifold. Significant deviation of the individual cylindertemperatures (e.g. >20° C.) indicates the presence of internal injectordeposits (IDIDs).

The tests (DU and CU) are each conducted with run time 8 h. The one-hourtest cycle from CEC F-098-08 is run through 8 times in each case. In theevent of deviations of the individual cylinder temperatures of greaterthan 45° C. from the mean for all 4 cylinders, the test is stoppedearly.

B. Preparation Examples Preparation Example 1 Preparation ofPolyisobutene Epoxide

To a solution of polyisobutene 1000 (300 g) in n-heptane (400 ml) areadded, at room temperature, formic acid (96.6 g) andmethyltrioctylammonium chloride (1.33 g). The reaction mixture is heatedto 75° C. and hydrogen peroxide solution (30%, 88.4 g) is slowly addeddropwise, in the course of which the temperature is kept at 75° C. Thereaction mixture is stirred at 75° C. for 10 h and cooled to roomtemperature, and the phases are separated. The organic phase is washedsuccessively with aqueous NaHSO₃ solution, saturated NaHCO₃ solution andwater. The organic phase is dried over Na₂SO₄ and the solvent is removedunder reduced pressure with the aid of a rotary evaporator. This givespolyisobutene epoxide (285 g).

Preparation Example 2 Polyisobutene Epoxide Quaternized withN-Methylpyrrolidine/Acetic Acid

Polyisobutene epoxide from preparation example 1 (30 g) is admixed withmethanol (36.1 g), and N-methylpyrrolidine (4.5 g) and acetic acid (1.6g) are added. The reaction mixture is transferred into an autoclave,inertized with nitrogen and stirred under autogenous pressure at 140° C.for 20 h. The reactor contents are discharged and volatile constituentsare removed under reduced pressure with the aid of a rotary evaporator.A MALDI-MS analysis of the reaction product thus obtained confirms theformation of the quaternary ammonium compound.

Preparation Example 3 1-Dodecene Oxide Quaternized withN-Methylpyrrolidine/Acetic Acid

A solution of 1-dodecene oxide (73.7 g) and N-methylpyrrolidine (97.2 g)in isopropanol (193.7 g) is admixed at 60° with acetic acid (22.8 g)within 10 minutes, and the reaction mixture thus obtained is stirred at60° C. for 14 h. Volatile constituents are removed under reducedpressure with the aid of a rotary evaporator. A ¹H NMR analysis (CDCl₃)of the reaction product thus obtained (124 g) confirms the formation ofthe quaternary ammonium compound (6 (NCH₃)=3.30 ppm).

Preparation Example 4 Mixture of 1-Dodecene Oxide, 1-Tetradecene Oxideand 1-Hexadecene Oxide, Quaternized with N-Methylpyrrolidine/Acetic Acid

A solution of 1-dodecene oxide (18.4 g), 1-tetradecene oxide (21.2 g),1-hexadecene oxide (24.0 g) and N-methylpyrrolidine (51.1 g) inisopropanol (133 g) is admixed at 60° with acetic acid (18.0 g) within10 minutes, and the reaction mixture obtained is stirred at 60° C. for15 h. Volatile constituents are removed under reduced pressure with theaid of a rotary evaporator. A ¹H NMR analysis (CDCl₃) of the reactionproduct thus obtained (102 g) confirms the formation of the quaternaryammonium compound (6 (NCH₃)=3.30 ppm).

Preparation Example 5 1-Dodecene Oxide Quaternized with NMe₃/Tall OilFatty Acid

In an autoclave, a solution of 1-dodecene oxide (19.4 g) in isopropanol(59.4 g) is admixed at room temperature with trimethylamine (11.8 g).The mixture is heated to 60° C. under autogenous pressure, and tall oilfatty acid (28.2 g) is metered in slowly and rinsed in with isopropanol(10 ml). The reaction mixture is stirred at 60° C. for a further 12 h.The reactor contents are cooled and volatile constituents are driven outwith a nitrogen stream. The solvent is subsequently removed underreduced pressure with the aid of a rotary evaporator. A ¹H NMR analysis(CDCl₃) of the reaction product thus obtained (53.4 g) confirms theformation of the quaternary ammonium compound (6 (N(CH₃)₃)=3.40 ppm).

Preparation Example 6 1-Dodecene Oxide Quaternized withN,N-Dimethylethanolamine/Tall Oil Fatty Acid

A solution of 1-dodecene oxide (73.6 g) and N,N-dimethylethanolamine(34.2 g) in isopropanol (214.8 g) is admixed at 60° C. with tall oilfatty acid (107 g) within 20 minutes, and the reaction mixture thusobtained is stirred at 60° C. for 22 h. Volatile constituents areremoved under reduced pressure with the aid of a rotary evaporator. A ¹HNMR analysis (CDCl₃) of the reaction product thus obtained (212 g)confirms the formation of the quaternary ammonium compound(N(CH₃)_(a))=3.33 ppm, N(CH₃)_(b))=3.34 ppm).

Preparation Example 7 1-Dodecene Oxide Quaternized with NMe₃/SalicylicAcid

In an autoclave, a solution of 1-dodecene oxide (23.9 g) in isopropanol(57.1 g) is admixed at room temperature with trimethylamine (15.3 g).The mixture is heated to 60° C. under autogenous pressure, and asolution of salicylic acid (17.9 g) in isopropanol (40 g) is metered inslowly and rinsed in with isopropanol (10 ml). The reaction mixture isstirred at 60° C. for a further 12 h. The reactor contents are cooledand volatile constituents are driven out with a nitrogen stream. Thesolvent is subsequently removed under reduced pressure with the aid of arotary evaporator. A ¹H NMR analysis (CDCl₃) of the reaction productthus obtained (47.5 g) confirms the formation of the quaternary ammoniumcompound (N(CH₃)₃)=3.26 ppm).

Preparation Example 8 1-Dodecene Oxide Quaternized withN,N-Dimethylethanolamine/Salicylic Acid

A solution of 1-dodecene oxide (73.6 g) and N,N-dimethylethanolamine(34.2 g) in isopropanol (160.3 g) is admixed at 60° C. with salicylicacid (52.4 g) within 20 minutes, and the reaction mixture thus obtainedis stirred at 60° C. for 23 h. Volatile constituents are removed underreduced pressure with the aid of a rotary evaporator. A ¹H NMR analysis(CDCl₃) of the reaction product thus obtained (154 g) confirms theformation of the quaternary ammonium compound (N(CH₃)_(a))=3.21 ppm,N(CH₃)_(b))=3.22 ppm).

C. Use Examples

In the use examples which follow, the additives are used either as apure substance (as synthesized in the above preparation examples) or inthe form of an additive package.

Use Example 1 Determination of Additive Action on the Formation ofDeposits in Diesel Engine Injection Nozzles a) XUD9 Tests

The results are summarized in Table 1.

TABLE 1 Results of the XUD9 tests Flow restriction 0.1 mm needle Dosagestroke Ex. Reference Fuel ppm active [%] #1 according to EN590-B7-1 4014.3 preparation example 3 #2 base value EN590-B7-1 0 72.5 #3 accordingto RF-06-03 60 52.9 preparation example 3 #4 base value RF-06-03 0 77.2#5 according to EN590-B7-1 40 7 preparation example 4 #6 according toEN590-B7-2 40 1.5 preparation example 5 #7 base value EN590-B7-2 0 73.2#8 according to RF-06-03 40 0 preparation example 2 #9 base valueRF-06-03 0 68

EN590-B7-1 and -2 are commercial diesel fuels to EN590 with maximumbiodiesel content 7% to DIN EN 14214.

b) DW10 Dirty-Up Clean-Up Test

TABLE 2 Results of the DW10 DU CU tests Dosage % power loss % power lossppm DU, see DU-CU, Ex. Reference Fuel active description see description#1 according to RF-06-03 105 4.1 −6.1 preparation example 4

Explicit reference is made to the disclosure of the publications citedherein.

1-15. (canceled)
 16. A reaction product comprising a quaternizednitrogen compound, said reaction product being obtainable by: reactingat least one hydrocarbyl epoxide of the general formula I:

in which at least one of the R₁ and R₂ radicals is a straight-chain orbranched, saturated or unsaturated, long-chain hydrocarbyl radicalhaving 7 to 50 carbon atoms and the other of the two radicals isoptionally H or a short-chain hydrocarbyl radical, selected fromstraight-chain or branched C₁-C₇-alkyl or C₂-C₇-alkanyl, optionallyinterrupted by one or more heteroatom groups, or optionally mono- orpolysubstituted; and the R₃ and R₄ radicals are the same or differentand are each H or a short-chain hydrocarbyl radical as defined above;with at least one tertiary amine of the general formula II:R_(a)R_(b)R_(c)N  (II) in which R_(a), R_(b) and R_(c) are eachindependently a straight-chain or branched, saturated or unsaturated,optionally substituted hydrocarbyl radical, or two of the R_(a), R_(b)and R_(c) radicals, together with the nitrogen atom to which they arebonded, form an optionally substituted 5- to 7-membered, saturated orunsaturated, nonaromatic or aromatic heterocyclic ring which mayoptionally bear at least one further ring heteroatom such as O, S or N;and in the presence of at least one acid of the formula III:H⁺A⁻  (III) in which A⁻ is the anion of at least one mono- orpoly-basic, inorganic or organic, natural or synthetic acid.
 17. Areaction product according to claim 16 which comprises at least onequaternized nitrogen compound having formula (IV), wherein formula IVis:

in which the R₁, R₂, R₃, R₄, R_(a), R_(b), and R_(c) radicals are eachas defined above and A is the anion of the monocarboxylic acid used. 18.The reaction product according to claim 16, wherein the acid is selectedfrom a) saturated or unsaturated, aliphatic or aromatic C₁-C₂₀monocarboxylic acids, or b) fatty acids selected from straight-chain orbranched, monounsaturated or polyunsaturated, optionally substitutedC₆-C₃₀ monocarboxylic acids.
 19. The reaction product according to claim16, wherein the reaction product comprises at least one compound of thegeneral formula IV:

in which the R₁, R₂, R₃, R₄, R_(a), R_(b), and R_(c) radicals are eachas defined above and A is the anion of a monocarboxylic acid.
 20. Thereaction product according to claim 16, wherein the amine of the generalformula II is selected from tri-C₁-C₂₄- or tri-C₄-C₁₂-alkylamines orcompounds of the general formula II in which one of the R_(a), R_(b) andR_(c) radicals is a C₁-C₄-alkyl radical and the two other radicals,together with the nitrogen atom to which they are bonded, form a 5- or6-membered heterocyclic saturated or unsaturated ring which mayoptionally bear at least one further ring heteroatom such as O, S or N.21. The reaction product according to claim 16, wherein the compound ofthe general formula I is a polyalkylene epoxide which is obtained byepoxidizing a polyalkylene, especially poly-(C₂-C₆)-alkylene, having anumber-average molecular weight (M_(n)) of 85 to 20
 000. 22. Thereaction product according to claim 21, wherein the polyalkylene is apolyisobutylene having a proportion of vinylidene double bonds ofgreater than 70 mol %.
 23. The reaction product according to claim 16,wherein the long-chain hydrocarbyl radical in the compounds of thegeneral formula I is a straight-chain or branched aliphatic hydrocarbylradical having 8 to
 40. 24. A method for reducing deposits in an intakesystem of a DISI or PFI (port fuel injector) engine or other gasolineengine comprising contacting said engine with a reaction productcomprising a quaternized nitrogen compound, or with a fraction thereofwhich comprises a quaternized nitrogen compound, which is obtained bypurification from the reaction product as defined in claim
 16. 25. Amethod for reducing deposits in an intake system of internal dieselinjector deposits (IDIDs) or other diesel engine and/or for reducingvalve sticking in direct injection diesel engines or in common railinjection systems comprising: contacting said engine with a reactionproduct comprising a quaternized nitrogen compound, or with a fractionthereof which comprises a quaternized nitrogen compound, which isobtained by purification from the reaction product as defined in claim16.
 26. A gasoline fuel additive comprising the reaction productaccording to claim
 16. 27. A diesel fuel additive comprising thereaction product according to claim 16.